CN102140115B - Flame-retardant plasticizer of methyl silicate trichloroethyl ester compound and preparation method thereof - Google Patents
Flame-retardant plasticizer of methyl silicate trichloroethyl ester compound and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a flame-retardant plasticizer of a methyl silicate trichloroethyl ester compound and a preparation method thereof, in particular to a methyl silicate tri(2-chloroethyl) ester compound and a preparation method thereof. The structure of the compound is shown as CH3Si(OCH2CH2Cl)3. The preparation method comprises the following steps of: mixing methyltrimethoxy silane and ethylene chlorohydrin in a certain molar ratio with an organic solvent by stirring; heating for refluxing; removing a fixed amount of methanol generated by a reaction by evaporating with a fractionating device; and purifying to obtain liquid methyl silicate trichloroethyl ester. The methyl silicate trichloroethyl ester obtained with the method has high flame retardance, high plasticity, a simple production process, small equipment investment and low cost, is environment-friendly and is easy for realizing industrial production.
Description
Technical field
The present invention relates to a kind of flame-retardant plasticizer methyl siliconic acid three chloro-ethyl ester compounds and preparation method thereof.Be specifically related to a kind of methyl siliconic acid three (2-chloroethyl) ester cpds and preparation method thereof.Methyl siliconic acid three chloro-ethyl esters belong to the organic silicon flame-retardant softening agent, are suitable for the fire-retardant plasticizer additives of SE, urethane, epoxy resin, unsaturated polyester etc.
Background technology
Because inflammable macromolecular material and softening agent number of applications, fire retardant has obtained fast development.The fire retardant consumption is the second largest auxiliary agent that is only second to plasticizer consumption at present.People always hope that from angle easy to use flame retardant resistance and plasticising performance embody in same compound structure, promptly synthetic flame-retardant plasticizer; Find that from use some material such as SE itself are the good flame materials; But because the adding of inflammable softening agent makes the inflammable of material change; Also, also inspire people to develop new flame-retardant plasticizer in order to overcome this problem promptly because the use of softening agent must add fire retardant simultaneously.The phosphorous flame-retardant softening agent is existing at present uses, and silicon is that flame-retardant plasticizer is owing to the Application and Development that costs an arm and a leg is restricted.The methyltrimethoxy silane that the inventor has researched and developed out with cheapness is raw material and glycol chlorohydrin prepared in reaction novel flame-retardant softening agent methyl siliconic acid three chloro-ethyl esters.The present invention has increased the flame-retardant plasticizer new variety that cheapness is good, the deficiency that can meet the need of market, has a good economic implications again.
Summary of the invention
One of the object of the invention is that simple, the fire-retardant plasticity of its synthesis technique is good, can overcome deficiency of the prior art with synthetic a kind of silicon halogen cooperative flame retardant plasticized compound methyl siliconic acid three chloro-ethyl esters of the most cheap methyltrimethoxy silane.
For realizing the foregoing invention purpose, the present invention has adopted following technical scheme:
A kind of methyl siliconic acid three chloro-ethyl ester compounds is characterized in that the structure of this compound is shown below:
CH
3Si(OCH
2CH
2Cl)
3
Another object of the present invention is to propose a kind of preparation method of three chloro-ethyl esters of methyl siliconic acid as stated, its technology is simple, be easy to large-scale production, and low in raw material cost is easy to get, and facility investment is few, and is with low cost, do not produce pollution, and this method is:
The methyltrimethoxy silane and the glycol chlorohydrin of certain mol proportion are mixed with YLENE; Make it to be warming up to 104 ℃ of backflows; And constantly steam the methyl alcohol that reaction generates through fractionation plant, along with the carrying out of reaction, reflux temperature is brought up to 140 ℃ gradually; The about 6h of return time, until the methyl alcohol that steams near theoretical amount.Then distilling off solvent and excessive glycol chlorohydrin (reclaim and use) and micro-low boilers through cooling, make methyl siliconic acid three chloro-ethyl esters.
This method also can be:
The methyltrimethoxy silane and the glycol chlorohydrin of certain mol proportion are mixed with chlorobenzene; Make it to be warming up to 104 ℃ of backflows; And constantly steam the methyl alcohol that reaction generates through fractionation plant, along with the carrying out of reaction, reflux temperature is brought up to 134 ℃ gradually; The about 8h of return time, until the methyl alcohol that steams near theoretical amount.Then distilling off solvent and excessive glycol chlorohydrin (reclaim and use) and micro-low boilers through cooling, make methyl siliconic acid three chloro-ethyl esters.
This method also can be:
The methyltrimethoxy silane and the glycol chlorohydrin of certain mol proportion are mixed with ethylene glycol diethyl ether; Make it to be warming up to 104 ℃ of backflows; And constantly steam the methyl alcohol that reaction generates through fractionation plant, along with the carrying out of reaction, reflux temperature is brought up to 122 ℃ gradually; The about 10h of return time, until the methyl alcohol that steams near theoretical amount.Then distilling off solvent and excessive glycol chlorohydrin (reclaim and use) and micro-low boilers through cooling, make methyl siliconic acid three chloro-ethyl esters.
This method also can be:
The methyltrimethoxy silane and the glycol chlorohydrin of certain mol proportion are mixed with toluene; Make it to be warming up to 104 ℃ of backflows; And constantly steam the methyl alcohol that reaction generates through fractionation plant, along with the carrying out of reaction, reflux temperature is brought up to 112 ℃ gradually; The about 12h of return time, until the methyl alcohol that steams near theoretical amount.Then distilling off solvent and excessive glycol chlorohydrin (reclaim and use) and micro-low boilers through cooling, make methyl siliconic acid three chloro-ethyl esters.
This method also can be:
The methyltrimethoxy silane and the glycol chlorohydrin of certain mol proportion are mixed with dioxane, make it to be warming up to 102 ℃ of backflows, the about 15h of return time, and constantly steam the methyl alcohol that reaction generates through fractionation plant, until the methyl alcohol that steams near theoretical amount.Then distilling off solvent and excessive glycol chlorohydrin (reclaim and use) and micro-low boilers through cooling, make methyl siliconic acid three chloro-ethyl esters.
Certain mol proportion is meant that the mol ratio of methyltrimethoxy silane and glycol chlorohydrin is 1: 3～1: 5 as stated.
Methyl siliconic acid three of the present invention (2-chloroethyl) ester is a colourless liquid, and its productive rate is 92%～97%, and decomposition temperature is 235 ± 5 ℃, and flash-point (open cup) is 195 ± 5 ℃.Density is 1.333 (20 ℃), refractive index n
D 25=1.4558, it is suitable as the usefulness of the fire retardant of materials such as SE, Z 150PH, epoxy resin, unsaturated polyester, urethane, and the synthesis technique principle of methyl siliconic acid three chloro-ethyl esters is shown below:
CH
3Si(OCH
3)
3+3HOC
3H
6Cl—→CH
3Si(OCH
2CH
2Cl)
3+3CH
3OH
Compared with prior art, beneficial effect of the present invention is:
1. because methyl estersil flame-retardant plasticizer of the present invention has stable C-Si bond structure and symmetric ester structure, its physical and chemical performance is stable, and plasticity is preferably arranged, and containing the dual ignition-proof element of silicon chlorine in the molecule simultaneously has flame retardant resistance preferably again.
2. the present invention is synthetic silicon halogen cooperative flame retardant softening agent methyl siliconic acid three chloro-ethyl esters of raw material with the methyltrimethoxy silane of cheapness, has developed cheap good flame-retardant plasticizer new variety.
3. preparation method of the present invention is simple, and low in raw material cost is easy to get, and cost is low, does not produce pollution, is easy to large-scale production.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described further.
Embodiment 1 is in being equipped with the 200ml four-hole boiling flask of whisking appliance, TM and fractionation plant; Add 0.1mol (13.6g) methyltrimethoxy silane and 0.3mol (24.2g) glycol chlorohydrin and 40ml YLENE, make it to be warming up to 104 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates through fractionation plant (the control column top temperature is not higher than 64 ℃); Carrying out along with reaction; Reflux temperature is brought up to 140 ℃ gradually, the about 7h of return time, until the methyl alcohol that steams near theoretical amount.Then distilling off solvent and excessive glycol chlorohydrin (reclaim and use) and low boilers through cooling, make methyl siliconic acid three chloro-ethyl esters, productive rate 92%.Its decomposition temperature is 235 ± 5 ℃, and flash-point (open cup) is 195 ± 5 ℃.Density is 1.333 (20 ℃), refractive index n
D 25=1.4558.
Embodiment 2 is in being equipped with the 200ml four-hole boiling flask of whisking appliance, TM and fractionation plant; Add 0.1mol (13.6g) methyltrimethoxy silane and 0.32mol (25.8g) glycol chlorohydrin and 40ml chlorobenzene, make it to be warming up to 104 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates through fractionation plant (the control column top temperature is not higher than 64 ℃); Carrying out along with reaction; Reflux temperature is brought up to 134 ℃ gradually, the about 8h of return time, until the methyl alcohol that steams near theoretical amount.Then distilling off solvent and excessive glycol chlorohydrin (reclaim and use) and low boilers through cooling, make methyl siliconic acid three chloro-ethyl esters, productive rate 95%.Its decomposition temperature is 235 ± 5 ℃, and flash-point (open cup) is 195 ± 5 ℃.Density is 1.333 (20 ℃), refractive index n
D 25=1.4558.
Embodiment 3 is in being equipped with the 200ml four-hole boiling flask of whisking appliance, TM and fractionation plant; Add 0.1mol (13.6g) methyltrimethoxy silane and 0.34mol (27.4g) glycol chlorohydrin and 40ml ethylene glycol diethyl ether, make it to be warming up to 104 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates through fractionation plant (the control column top temperature is not higher than 64 ℃); Carrying out along with reaction; Reflux temperature is brought up to 122 ℃ gradually, the about 10h of return time, until the methyl alcohol that steams near theoretical amount.Then distilling off solvent and excessive glycol chlorohydrin (reclaim and use) and low boilers through cooling, make methyl siliconic acid three chloro-ethyl esters, productive rate 96%.Its decomposition temperature is 235 ± 5 ℃, and flash-point (open cup) is 195 ± 5 ℃.Density is 1.333 (20 ℃), refractive index n
D 25=1.4558.
Embodiment 4 is in being equipped with the 200ml four-hole boiling flask of whisking appliance, TM and fractionation plant; Add 0.1mol (13.6g) methyltrimethoxy silane and 0.36mol (29g) glycol chlorohydrin and 40ml toluene, make it to be warming up to 104 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates through fractionation plant (the control column top temperature is not higher than 64 ℃); Carrying out along with reaction; Reflux temperature is brought up to 112 ℃ gradually, the about 11h of return time, until the methyl alcohol that steams near theoretical amount.Then distilling off solvent and excessive glycol chlorohydrin (reclaim and use) and low boilers through cooling, make methyl siliconic acid three chloro-ethyl esters, productive rate 96%.Its decomposition temperature is 235 ± 5 ℃, and flash-point (open cup) is 195 ± 5 ℃.Density is 1.333 (20 ℃), refractive index n
D 25=1.4558.
Embodiment 5 is in being equipped with the 200ml four-hole boiling flask of whisking appliance, TM and fractionation plant; Add 0.1mol (13.6g) methyltrimethoxy silane and 0.4mol (32.2g) glycol chlorohydrin and 40ml toluene, make it to be warming up to 104 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates through fractionation plant (the control column top temperature is not higher than 64 ℃); Carrying out along with reaction; Reflux temperature is brought up to 112 ℃ gradually, the about 12h of return time, until the methyl alcohol that steams near theoretical amount.Then distilling off solvent and excessive glycol chlorohydrin (reclaim and use) and low boilers through cooling, make methyl siliconic acid three chloro-ethyl esters, productive rate 97%.
Embodiment 6 is in being equipped with the 200ml four-hole boiling flask of whisking appliance, TM and fractionation plant; Add 0.1mol (13.6g) methyltrimethoxy silane and 0.5mol (40.3g) glycol chlorohydrin and 40ml dioxane, make it to be warming up to 102 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates through fractionation plant (the control column top temperature is not higher than 64 ℃); Carrying out along with reaction; Reflux temperature is brought up to 102 ℃ gradually, the about 14h of return time, until the methyl alcohol that steams near theoretical amount.Then distilling off solvent and excessive glycol chlorohydrin (reclaim and use) and low boilers through cooling, make methyl siliconic acid three chloro-ethyl esters, productive rate 97%.Its decomposition temperature is 235 ± 5 ℃, and flash-point (open cup) is 195 ± 5 ℃.Density is 1.333 (20 ℃), refractive index n
D 25=1.4558.
The routine main technologic parameters of subordinate list 1 preparation
This case contriver also is applied to above-mentioned synthetic methyl siliconic acid three chloro-ethyl esters in the SE.The limiting oxygen index(LOI) of reference: GB/T2406-2008 " plastics combustibility test method-oxygen index method " test sample article.After getting methyl siliconic acid three chloro-ethyl esters, plasticizer phthalic acid dioctyl ester, synergistic flame retardant Antimony Trioxide: 99.5Min and SE and mixing in varing proportions; Extrude with forcing machine; Process the batten that diameter is 3mm; And its flame retardant properties tested, it is as shown in table 2 below to have listed the part test result:
The flame retardant properties data of table 2 methyl siliconic acid three chloro-ethyl esters
Claims (5)
1. the preparation method of flame-retardant plasticizer methyl siliconic acid three chloro-ethyl esters is characterized in that, this method is: stir down; The methyltrimethoxy silane and the glycol chlorohydrin of certain mol proportion are mixed with organic solvent, make it to be warming up to backflow, and constantly steam the methyl alcohol that reaction generates through fractionation plant; Carrying out along with reaction; Temperature of reaction is brought up to the suitable reflux temperature of mixture gradually, the insulation back flow reaction for some time, until the methyl alcohol that steams near theoretical amount; Reaction finishes, and then purified processing makes colourless to light yellow liquid methyl siliconic acid three chloro-ethyl esters;
Said methyl siliconic acid three chloro-ethyl esters are applicable as silicon halogen dual element cooperative flame retardant softening agent, and it has following structure:
CH
3Si(OCH
2CH
2Cl)
3。
2. the preparation method of methyl siliconic acid three chloro-ethyl esters according to claim 1, it is characterized in that: said certain mol proportion is meant that the mol ratio of methyltrimethoxy silane and glycol chlorohydrin is 1: 3～1: 5.
3. the preparation method of methyl siliconic acid three chloro-ethyl esters according to claim 1 is characterized in that: the suitable reflux temperature that said temperature of reaction is brought up to mixture gradually is for being 102 ℃～140 ℃ according to different solvents and different mol ratios.
4. the preparation method of methyl siliconic acid three chloro-ethyl esters according to claim 1, it is characterized in that: said insulation back flow reaction for some time is 6～15h.
5. the preparation method of methyl siliconic acid three chloro-ethyl esters according to claim 1 is characterized in that: said purification process is for after reaction finishes, distilling off solvent and excessive glycol chlorohydrin and micro-low boilers.
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| CN104710462A (en) * | 2015-03-06 | 2015-06-17 | 苏州阳桥化工科技有限公司 | Preparation method of dimethyl ethylenedioxy ring silanization compound serving as fire retardant |
| CN104710463A (en) * | 2015-03-06 | 2015-06-17 | 苏州阳桥化工科技有限公司 | Preparation method of dimethyl-1,2-o- dioxygen base ring silanization compound serving as flame resistant plastifier |
| CN104744503B (en) * | 2015-03-06 | 2017-09-29 | 苏州科技大学 | Fire retardant dimethyl silicic acid dibromoneopentyl glycol ester compounds and preparation method thereof |
| CN104650138A (en) * | 2015-03-06 | 2015-05-27 | 苏州阳桥化工科技有限公司 | Preparation method of flame retardant, namely dimethyl-1, 3-propdioxyl cyclic silane compound |
| CN104725412A (en) * | 2015-03-06 | 2015-06-24 | 苏州阳桥化工科技有限公司 | Preparation method of fire-retardant plasticizer dimethyl-1,3-m-dioxo cyclosilane compound |
| CN104710460A (en) * | 2015-03-06 | 2015-06-17 | 苏州阳桥化工科技有限公司 | Preparation method of dimethyl dibromo neopentyl dioxy cyclosilane compound as fire retardant |
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Non-Patent Citations (1)
| Title |
|---|
| Von Hoang Thi Phung, Pham Ba Chi und F. Kober.Synthese anorganischer Tintenfisch-Molekule.《Z. anorg.allg.chem》.1981,(第472期),第75-82页. * |
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